Composition containing polyion complex particles and filler

Abstract

To provide a composition that can provide an improved moisturizing texture, preferably a combination of an improved moisturizing texture and an improved mat feeling.SOLUTION: The present invention relates to a composition comprising: (a) at least one particle, comprising at least one cationic polymer and at least one anionic polymer, and at least one non-polymeric acid having two or more pKa values or salt(s) thereof; (b) at least one filler; and (c) water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising polyion complex particles and a filler, and a cosmetic method using the composition. [Background technology]

[0002] It is known that the oily or sticky skin caused by sebum can accentuate roughness of the skin. In other words, oily skin can make roughness of the skin, such as pores and wrinkles, more noticeable. Therefore, cosmetic users desire to achieve a matte appearance on their skin.

[0003] There are several oil-absorbing powders that can be used in cosmetics to provide a mattifying effect to the skin by absorbing sebum with these powders.

[0004] However, oil-absorbing powders often result in an undesirable dry or squeaky feel even in cosmetics containing water, in other words, it is often difficult to use oil-absorbing powders in cosmetics containing water to provide a good moisturizing texture.

[0005] The above-mentioned problems are not limited to oil-absorbing powders. For example, the use of fillers in cosmetics can cause a squeaky texture, and even if the cosmetics contain water, they may not be able to achieve a good moisturizing texture. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application No. 0080976 [Patent Document 2] French Patent No. 2077143 [Patent Document 3] French Patent No. 2393573 [Patent Document 4] French Patent No. 1492597 [Patent Document 5] U.S. Patent No. 4,131,576 [Patent Document 6] U.S. Patent No. 3,589,578 [Patent Document 7] U.S. Patent No. 4,031,307 [Patent Document 8] French Patent No. 2162025 [Patent Document 9] French Patent No. 2280361 [Patent Document 10] French Patent No. 2252840 [Patent Document 11] French Patent No. 2368508 [Patent Document 12] French Patent No. 1583363 [Patent Document 13] U.S. Patent No. 3,227,615 [Patent Document 14] U.S. Patent No. 2,961,347 [Patent Document 15] French Patent No. 2080759 [Patent Document 16] French Patent No. 2190406 [Patent Document 17] French Patent No. 2320330 [Patent Document 18] French Patent No. 2270846 [Patent Document 19] French Patent No. 2316271 [Patent Document 20] French Patent No. 2336434 [Patent Document 21] French Patent No. 2413907 [Patent Document 22] U.S. Patent No. 2,273,780 [Patent Document 23] U.S. Patent No. 2,375,853 [Patent Document 24] U.S. Patent No. 2,388,614 [Patent Document 25] U.S. Patent No. 2,454,547 [Patent Document 26] U.S. Patent No. 3,206,462 [Patent Document 27] U.S. Patent No. 2,261,002 [Patent Document 28] U.S. Patent No. 2,271,378 [Patent Document 29] U.S. Patent No. 3,874,870 [Patent Document 30] U.S. Patent No. 4,001,432 [Patent Document 31] U.S. Patent No. 3,929,990 [Patent Document 32] U.S. Patent No. 3,966,904 [Patent Document 33] U.S. Patent No. 4,005,193 [Patent Document 34] U.S. Patent No. 4,025,617 [Patent Document 35] U.S. Patent No. 4,025,627 [Patent Document 36] U.S. Patent No. 4,025,653 [Patent Document 37] U.S. Patent No. 4,026,945 [Patent Document 38] U.S. Patent No. 4,027,020 [Patent Document 39] European Patent Application No. 0122324 [Patent Document 40] EP-A-0750899 [Patent Document 41] EP-A-1069172 [Patent Document 42] EP-A-0173109 [Patent Document 43] U.S. Patent No. 7,470,725 [Patent Document 44] JP-A-2014-088307 [Patent Document 45] JP-A-2014-218433 [Patent Document 46] JP-A-2018-177620 [Non-licensed literature]

[0007] [Non-licensed Document 1] Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Volume 33, No. 10-3694~3704 [Non-licensed Document 2] "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699~715 [Non-licensed Document 3] D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998), pages 2101~2127 [Non-licensed Document 4] Brinker CJ and Scherer GW, Sol-Gel Science, New York, Academic Press, 1990 [Non-licensed Document 5] The Journal of the American Chemical Society, Volume 60, Page 309, February 1938 [Non-licensed Document 6] Van de Hulst, HC, "Light Scattering by Small Particles", Chapters 9 and 10, Wiley, New York, 1957 [Non-licensed Document 7] Barrett, EP; Joyner, LG; Halenda, PP, J. Am. Chem. Soc. 73, 373 (1951) [Non-patent document 8] Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press [Non-Patent Document 9] Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, there is a need for compositions that contain fillers yet can provide an improved moisturizing texture.

[0009] It is therefore an object of the present invention to provide a composition that can provide an improved moisturizing feel, preferably both an improved moisturizing feel and a matte feel-imparting effect. [Means for solving the problem]

[0010] The above object of the present invention is to (a) Below: at least one cationic polymer and at least one anionic polymer; and At least one non-polymeric acid or salt thereof having two or more pKa values At least one particle comprising: (b) at least one filler; (c) Water and This can be achieved by a composition comprising:

[0011] The cationic polymer may have at least one positively charged and / or positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups.

[0012] The cationic polymer may be selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as collagen, cationic cellulose polymers, and salts thereof.

[0013] The amount of the (a) particle-forming cationic polymer in the composition according to the present invention can be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0014] The anionic polymer may be selected from hyaluronic acid and its derivatives.

[0015] The amount of the anionic polymer forming the particles (a) in the composition according to the present invention can be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0016] The non-polymeric acid or salt thereof having two or more pKa values ​​may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof, more preferably phytic acid or salt thereof.

[0017] The amount of the non-polymeric acid or salt thereof having two or more pKa values ​​that forms the particles (a) in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, based on the total mass of the composition.

[0018] The amount of the (a) particles in the composition according to the present invention may be 0.01% to 15% by mass, preferably 0.05% to 10% by mass, and more preferably 0.1% to 5% by mass, relative to the total mass of the composition.

[0019] (b) The filler can be selected from hydrophilic or hydrophobic oil-absorbing powders. The hydrophobic oil-absorbing powder can be selected from hydrophobic silica, preferably hydrophobic silica aerogel, more preferably hydrophobic silica silylate aerogel powder.

[0020] The amount of the (b) filler in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0021] The amount of (c) water in the composition according to the present invention can be 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% by mass, relative to the total mass of the composition.

[0022] The composition according to the present invention may be a cosmetic composition, preferably a dermocosmetic composition, more preferably a skin care cosmetic composition.

[0023] The present invention also provides a cosmetic method for keratinous materials such as skin, comprising the steps of: applying a composition according to the invention to keratinous materials; drying the composition to form a cosmetic film on the keratinous material; The present invention also relates to a method comprising: DETAILED DESCRIPTION OF THE INVENTION

[0024] As a result of intensive research, the present inventors have discovered that it is possible to provide a composition that can provide an improved moisturizing texture, preferably a combination of an improved moisturizing texture and a matte feel-imparting effect.

[0025] Therefore, the composition according to the present invention (a) Below: at least one cationic polymer and at least one anionic polymer; and At least one non-polymeric acid or salt thereof having two or more pKa values At least one type of particle comprising (b) at least one filler; (c) Water and Includes:

[0026] Compositions according to the present invention may provide an improved or enhanced moisturizing texture, for example a better wet feel.

[0027] The improved moisturizing texture can be attributed to the presence of (a) particles in the composition according to the present invention.

[0028] Additionally, the compositions according to the present invention can reduce or prevent squeaky texture.

[0029] If the filler is oil-absorbing, the composition according to the present invention can absorb sebum. Therefore, the composition according to the present invention can reduce the shine on keratinous materials such as skin, and can reduce the appearance of roughness on the skin, such as pores and wrinkles. Accordingly, the composition according to the present invention can provide an optical matte effect while providing an improved moisturizing feel. Therefore, the composition according to the present invention can provide both an improved moisturizing feel and an optical matte effect. The optical matte effect is thought to be achieved immediately after applying the composition according to the present invention and / or is thought to last for a long time.

[0030] The compositions and methods according to the present invention will be described in more detail below.

[0031] [Polyion complex particles] The composition according to the present invention comprises at least one type of (a) particles, which are polyion complex particles. Two or more different types of (a) particles may be used in combination. Thus, a single type of (a) particle or a combination of different types of (a) particles may be used.

[0032] The particle size of the polyion complex particles may be 5 nm to 100 μm, preferably 100 nm to 50 μm, more preferably 200 nm to 40 μm, and even more preferably 500 nm to 30 μm. Particle sizes less than 1 μm can be measured by dynamic light scattering, and particle sizes greater than 1 μm can be measured by optical microscopy. This particle size may be based on the number average diameter.

[0033] The amount of (a) particles in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, relative to the total weight of the composition.

[0034] The amount of (a) particles in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, relative to the total weight of the composition.

[0035] The amount of the (a) particles in the composition according to the present invention may be 0.01% to 15% by mass, preferably 0.05% to 10% by mass, and more preferably 0.1% to 5% by mass, relative to the total mass of the composition.

[0036] When the composition according to the present invention includes (d) at least one oil as described below, a plurality of (a) particles can exist at the interface between (c) water and (d) oil. Thus, the (a) particles can stabilize an emulsion. For example, when (c) water constitutes the continuous phase and (d) oil constitutes the dispersed phase, the (a) particles can form an O / W emulsion that can resemble a so-called Pickering emulsion.

[0037] Alternatively, a plurality of (a) particles can form a capsule having a hollow space. At least one (d) oil can be present within the hollow space. In other words, the (d) oil can be incorporated into the capsule. The capsule wall can be composed of a continuous layer or film formed from the (a) particles. Without wishing to be bound by theory, it is believed that the (a) particles can reorganize at the interface between (c) water and (d) oil to spontaneously form a capsule having a hollow space for containing the (d) oil. For example, a continuous phase composed of (c) water and a dispersed phase composed of (d) oil in a capsule can form an O / W emulsion, which can also resemble a so-called Pickering emulsion.

[0038] The above is taken to mean that (a) the particles themselves are amphiphilic: (a) the particles themselves are insoluble in oil or water.

[0039] (a) The particles comprise at least one cationic polymer and at least one anionic polymer.

[0040] The types of cationic and anionic polymers are not limited. Two or more different types of cationic polymers may be used in combination. Therefore, a single type of cationic polymer or a combination of different types of cationic polymers may be used. Two or more different types of anionic polymers may be used in combination. Therefore, a single type of anionic polymer or a combination of different types of anionic polymers may be used.

[0041] The amount of cationic polymer / anionic polymer, for example, the ratio of chemical equivalents, may be 0.05 to 18, preferably 0.1 to 10, and more preferably 0.5 to 5.0. Specifically, it may be preferable that the ratio of the number of cationic groups in the cationic polymer to the number of anionic groups in the anionic polymer is 0.05 to 18, more preferably 0.1 to 10, and even more preferably 0.5 to 5.0.

[0042] The total amount of cationic and anionic polymers in the composition according to the invention may be 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more, relative to the total weight of the composition.

[0043] The total amount of cationic and anionic polymers in the composition according to the invention may be up to 30% by weight, preferably up to 25% by weight, more preferably up to 20% by weight, relative to the total weight of the composition.

[0044] The total amount of cationic and anionic polymers in the composition according to the present invention may be from 0.1% to 30% by weight, preferably from 0.5% to 25% by weight, more preferably from 1% to 20% by weight, relative to the total weight of the composition.

[0045] (cationic polymer) The cationic polymer has a positive charge density of 0.01 meq / g to 20 meq / g, preferably 0.05 to 15 meq / g, and more preferably 0.1 to 10 meq / g.

[0046] It may be preferable that the molecular weight of the cationic polymer is 500 or more, preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more.

[0047] Unless otherwise defined herein, "molecular weight" means number average molecular weight.

[0048] The cationic polymer may have at least one positively charged moiety selected from the group consisting of primary, secondary or tertiary amino groups, quaternary ammonium groups, guanidine groups, biguanide groups, imidazole groups, imino groups and pyridyl groups. The term "(primary) amino group" as used herein means an -NH group.

[0049] The cationic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

[0050] The cationic polymer can be selected from natural and synthetic cationic polymers. Non-limiting examples of cationic polymers are:

[0051] (1) Derived from esters and amides of acrylic or methacrylic acid, the formula:

[0052] [ka]

[0053] (In the formula, R1 and R2 may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 6 carbon atoms, such as methyl and ethyl groups; R3 may be the same or different and is selected from hydrogen and CH3; the symbols A may be the same or different and are selected from linear or branched alkyl groups containing 1 to 6 carbon atoms, for example 2 to 3 carbon atoms, and hydroxyalkyl groups containing 1 to 4 carbon atoms; R4, R5 and R6 may be the same or different and are selected from alkyl groups containing 1 to 18 carbon atoms and benzyl groups, and in at least one embodiment are alkyl groups containing 1 to 6 carbon atoms; Homopolymers and copolymers containing at least one unit selected from units of anions derived from inorganic or organic acids, such as methosulfate anions and halide ions, for example chloride and bromide ions.

[0054] The copolymers of family (1) above may also contain at least one unit derived from a comonomer, which may be chosen from acrylamide, methacrylamide, diacetone acrylamide, acrylamides and methacrylamides whose nitrogen atoms are substituted with (C1-C4) lower alkyl groups, groups derived from acrylic or methacrylic acid and their esters, vinyl lactams such as vinylpyrrolidone and vinylcaprolactam, and vinyl esters.

[0055] Examples of family (1) copolymers include, but are not limited to: Copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide; Copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, such as those described in European Patent Application No. 0 080 976; Copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, Quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, such as those described in French Patents Nos. 2 077 143 and 2 393 573; Dimethylaminoethyl methacrylate / vinyl caprolactam / vinyl pyrrolidone terpolymer, Vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymer, quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer, and Crosslinked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium salt polymers, such as those obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or by copolymerization of acrylamide and dimethylaminoethyl methacrylate quaternized with methyl chloride, followed by crosslinking with a compound containing olefinic unsaturation, such as methylenebisacrylamide.

[0056] (2) Cationic cellulose polymers, such as cellulose ether derivatives containing one or more quaternary ammonium groups, as described in French Patent No. 1 492 597, such as the polymers sold by Union Carbide Corporation under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as quaternary ammonium hydroxyethyl celluloses reacted with epoxides substituted with trimethylammonium groups.

[0057] The cationic cellulose polymer preferably has at least one quaternary ammonium group, preferably a quaternary trialkylammonium group, more preferably a quaternary trimethylammonium group.

[0058] The quaternary ammonium group has the following chemical formula (I):

[0059] [ka]

[0060] (In the formula, R1 and R2 each represent a C1-C3 alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; R3 is C1~C 24 represents an alkyl group, preferably a methyl group or an ethyl group, more preferably a methyl group; X- represents an anion, preferably a halide ion, more preferably a chloride ion; n represents an integer of 0 to 30, preferably 0 to 10, and more preferably 0; R4 represents a C1-C4 alkylene group, preferably an ethylene group or a propylene group. The quaternary ammonium group may be present in a group containing quaternary ammonium groups, which may be represented by the formula:

[0061] The leftmost ether bond (-O-) in the above chemical formula (I) can be attached to the sugar ring of a polysaccharide.

[0062] The quaternary ammonium group-containing group is -O-CH2-CH(OH)-CH2-N + It is preferably (CH3)3.

[0063] (3) Cationic cellulose polymers such as cellulose copolymers and cellulose derivatives grafted with quaternary ammonium water-soluble monomers, as described in U.S. Pat. No. 4,131,576, for example, hydroxyalkyl celluloses grafted with salts selected from methacryloylethyltrimethylammonium, methacrylamidepropyltrimethylammonium, and dimethyldiallylammonium salts, such as hydroxymethyl-, hydroxyethyl-, and hydroxypropylcellulose.

[0064] Commercially available products corresponding to these polymers include, for example, those sold under the names "Celquat® L 200" and "Celquat® H 100" by National Starch.

[0065] (4) Non-cellulosic cationic polysaccharides, such as guar gum containing cationic trialkylammonium groups, cationic hyaluronic acid, and dextran hydroxypropyltrimonium chloride, as described in U.S. Patent Nos. 3,589,578 and 4,031,307. Salt-modified guar gum, such as 2,3-epoxypropyltrimethylammonium salt, for example, chloride-modified guar gum (guar hydroxypropyltrimonium chloride), can also be used.

[0066] Such products are, for example, sold by the company MEYHALL under the trade names JAGUAR® C13 S, JAGUAR® C15, JAGUAR® C17 and JAGUAR® C162.

[0067] (5) Polymers containing piperazinyl units and divalent alkylene or hydroxyalkylene groups, containing linear or branched chains optionally interrupted by at least one element selected from oxygen, sulfur, nitrogen, aromatic rings and heterocyclic rings, as well as the oxidation and / or quaternization products of these polymers. Such polymers are described, for example, in French Patents Nos. 2,162,025 and 2,280,361.

[0068] (6) Water-soluble polyaminoamides, for example, prepared by polycondensation of acidic compounds with polyamines, which may be crosslinked with an element selected from epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides, bisunsaturated derivatives, bishalohydrins, bisazetidinium compounds, bishaloacyldiamines, bisalkylhalides, and oligomers obtained by reacting bifunctional compounds reactive with elements selected from bishalohydrins, bisazetidinium compounds, bishaloacyldiamines, bisalkylhalides, epihalohydrins, diepoxides, and bisunsaturated derivatives; the crosslinking agent is used in an amount ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides may optionally be alkylated or, if they contain at least one tertiary amine function, may be quaternized. Such polymers are described, for example, in French Patents Nos. 2,252,840 and 2,368,508.

[0069] (7) Polyaminoamide derivatives obtained by condensing polyalkylenepolyamines with polycarboxylic acids followed by alkylation with bifunctional agents, such as adipic acid / dialkylaminohydroxyalkyldialkylenetriamine polymers, in which the alkyl groups contain 1 to 4 carbon atoms, such as methyl, ethyl, and propyl groups, and the alkylene groups contain 1 to 4 carbon atoms, such as ethylene groups. Such polymers are described, for example, in French Patent No. 1,583,363. In at least one embodiment, these derivatives can be chosen from adipic acid / dimethylaminohydroxypropyldiethylenetriamine polymers.

[0070] (8) Polymers obtained by reacting a polyalkylenepolyamine containing two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio of polyalkylenepolyamine to dicarboxylic acid can be in the range of 0.8:1 to 1.4:1, and the resulting polyaminoamide is reacted with epichlorohydrin in a molar ratio of epichlorohydrin to secondary amine groups of polyaminoamide in the range of 0.5:1 to 1.8:1. Such polymers are described, for example, in U.S. Patents 3,227,615 and 2,961,347.

[0071] (9) Cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as homopolymers and copolymers containing, as the main chain building block, at least one unit selected from units of the following formulae (Ia) and (Ib):

[0072] [ka]

[0073] (In the formula, k and t may be identical or different and are equal to 0 or 1, the sum k+t is equal to 1; R 12 is selected from hydrogen and a methyl group; R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 6 carbon atoms, hydroxyalkyl groups in which the alkyl group contains, for example, 1 to 5 carbon atoms, and lower (C1-C4) amidoalkyl groups, or R 10 and R 11 may, together with the nitrogen atom to which they are attached, form a heterocyclic group, such as piperidinyl and morpholinyl; Y' is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, and phosphate.) These polymers are described, for example, in French Patent No. 2 080 759 and its addition No. 2 190 406.

[0074] In one embodiment, R 10 and R 11 may be the same or different and are selected from alkyl groups containing 1 to 4 carbon atoms.

[0075] Examples of such polymers include, but are not limited to, (co)polydiallyldialkylammonium chlorides, such as the dimethyldiallylammonium chloride homopolymer sold under the name "MERQUAT® 100" by CALGON (and its homologues with lower mass average molecular weights), and the copolymer of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT® 550."

[0076] A quaternary diammonium polymer comprising at least one repeat unit of formula (II):

[0077] [ka]

[0078] {In the formula, R 13 , R 14 , R 15 and R 16 may be the same or different and are selected from aliphatic, alicyclic and arylaliphatic groups containing 1 to 20 carbon atoms, and lower hydroxyalkyl aliphatic groups; or R 13 , R 14 , R 15 and R 16 may together with or separately from the nitrogen atom to which they are attached form a heterocycle optionally containing a second heteroatom other than nitrogen, or R13 , R 14 , R 15 and R 16 may be the same or different and may be a nitrile group, an ester group, an acyl group, an amide group, -CO-OR 17 -E group and -CO-NH-R 17 -E group [wherein, R 17 is an alkylene group, and E is a quaternary ammonium group; A1 and B1 may be the same or different and are selected from polymethylene groups containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked to or inserted in the main chain, at least one element selected from aromatic rings, oxygen, sulfur, sulfoxide groups, sulfone groups, disulfide groups, amino groups, alkylamino groups, hydroxyl groups, quaternary ammonium groups, ureido groups, amide groups and ester groups; X - is an anion derived from an inorganic or organic acid, A1, R 13 and R 15 may be taken together with the two nitrogen atoms to which they are attached to form a piperazine ring; When A1 is selected from linear or branched, saturated or unsaturated alkylene or hydroxyalkylene groups, B1 can be selected from: -(CH2) n -CO-E'-OC-(CH2) n - wherein E′ is one of the following: a) OZO-, wherein Z is a linear or branched hydrocarbon-based group and a group of the following formula: -(CH2-CH2-O) x -CH2-CH2- -[CH2-CH(CH3)-O] y -CH2-CH(CH3)- wherein x and y may be the same or different and are selected from integers ranging from 1 to 4 representing a unique defined degree of polymerization, and numbers ranging from 1 to 4 representing an average degree of polymerization), b) bis-secondary diamine residues, such as piperazine derivatives; c) bis-primary diamine residues of the formula -NH-Y-NH-, where Y is selected from linear or branched hydrocarbon-based groups and the divalent group -CH-CH-SS-CH-CH-, and d) a ureylene group of the formula -NH-CO-NH- selected from]}.

[0079] In at least one embodiment, X - is an anion, such as chloride or bromide.

[0080] Polymers of this type are described, for example, in French Patents Nos. 2320330, 2270846, 2316271, 2336434, and 2413907, and in U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261, 002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945, and 4,027,020.

[0081] Non-limiting examples of such polymers include those comprising at least one repeat unit of formula (III):

[0082] [ka]

[0083] (In the formula, R 13 , R 14 , R 15 and R 16may be the same or different and are selected from alkyl and hydroxyalkyl groups containing 1 to 4 carbon atoms, n and p may be the same or different and are integers ranging from 2 to 20, and X - is an anion derived from an inorganic or organic acid).

[0084] (11) Polyquaternary ammonium polymers comprising units of formula (IV):

[0085] [ka]

[0086] (In the formula, R 18 , R 19 , R 20 and R 21 may be the same or different and are hydrogen, methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, -CH2CH2(OCH2CH2) p OH group (wherein p is an integer selected from the range of 0 to 6), provided that R 18 , R 19 , R 20 and R 21 and hydrogen at the same time, r and s may be the same or different and are selected from integers ranging from 1 to 6; q is selected from an integer ranging from 0 to 34; X - is an anion, for example a halide ion, A is selected from a dihalide group and a -CH2-CH2-O-CH2-CH2- group.

[0087] Such compounds are described, by way of example, in European Patent Application No. 0122324.

[0088] (12) Quaternary polymers of vinylpyrrolidone and vinylimidazole. Other examples of suitable cationic polymers include, but are not limited to, cationic proteins and cationic protein hydrolysates, polyalkyleneimines such as polyethyleneimine, polymers containing units selected from vinylpyridine units and vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes, and chitin derivatives.

[0089] According to one embodiment of the present invention, the at least one cationic polymer is chosen from cellulose ether derivatives containing quaternary ammonium groups, such as the product sold under the name "JR 400" by UNION CARBIDE CORPORATION, cationic cyclopolymers, such as the homopolymers and copolymers of dimethyldiallylammonium chloride sold under the names MERQUAT® 100, MERQUAT® 550 and MERQUAT® S by CALGON, guar gum modified with 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers of vinylpyrrolidone and vinylimidazole.

[0090] (13) Polyamines It is also possible to use as cationic polymers (co)polyamines, which may be homopolymers or copolymers containing multiple amino groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the (co)polyamine or, if present, in pendant groups.

[0091] Examples of (co)polyamines include chitosan, (co)polyallylamine, (co)polyvinylamine, (co)polyaniline, (co)polyvinylimidazole, (co)polydimethylaminoethylene methacrylate, (co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridine, (co)polyimines such as (co)polyethyleneimine, (co)polypyridines such as (co)poly(quaternary pyridine), (co)polybiguanides such as (co)polyaminopropylbiguanide, (co)polylysine, (co)polyornithine, (co)polyarginine, (co)polyhistidine, aminodextran, aminocellulose, amino(co)polyvinyl acetal, and salts thereof.

[0092] As the (co)polyamine, it is preferable to use (co)polylysine. Polylysine is well known. Polylysine can be a natural homopolymer of L-lysine that can be produced by bacterial fermentation. For example, polylysine can be ε-poly-L-lysine, which is typically used as a natural preservative in foods. Polylysine is a polyelectrolyte that is soluble in polar solvents such as water, propylene glycol, and glycerol. Polylysine is commercially available in various forms, such as poly-D-lysine and poly-L-lysine. Polylysine can be in the form of a salt and / or a solution.

[0093] (14) Cationic polyamino acids As the cationic polymer, it may be possible to use cationic polyamino acids, which may be cationic homopolymers or copolymers having multiple amino and carboxyl groups. The amino groups may be primary, secondary, tertiary, or quaternary amino groups. The amino groups may be present in the polymer backbone of the cationic polyamino acid or, if present, in pendant groups. The carboxyl groups may be present in pendant groups of the cationic polyamino acid, if present.

[0094] Examples of cationic polyamino acids include cationized collagen, cationized gelatin, steardimonium hydroxypropyl hydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheat protein, hydroxypropyltrimonium hydrolyzed conchiolin protein, steardimonium hydroxypropyl hydrolyzed soy protein, hydroxypropyltrimonium hydrolyzed soy protein, and cocodimonium hydroxypropyl hydrolyzed soy protein.

[0095] The following description relates to preferred embodiments of the cationic polymer.

[0096] It may be preferred that the cationic polymer is selected from cationic starches.

[0097] Examples of cationic starches include starches modified with 2,3-epoxypropyltrimethylammonium salts (e.g. chloride), such as the product known as Starch Hydroxypropyltrimonium Chloride according to the INCI name sold by Ondeo under the name SENSOMER Cl-50 or by Ingredion under the name Pencare™ DP 1015.

[0098] It may also be preferred that the cationic polymer is selected from cationic gums.

[0099] The gum may be selected, for example, from the group consisting of cassia gum, karaya gum, konjac gum, tragacanth gum, tara gum, acacia gum, and gum arabic.

[0100] Examples of cationic gums include cationic polygalactomannan derivatives, such as guar gum derivatives and cassia gum derivatives, such as CTFA: guar hydroxypropyltrimonium chloride, hydroxypropyl guar hydroxypropyltrimonium chloride, and cassia hydroxypropyltrimonium chloride. Guar hydroxypropyltrimonium chloride is commercially available from Rhodia Inc. under the Jaguar™ series and from Ashland Inc. under the N-Hance™ series. Cassia hydroxypropyltrimonium chloride is commercially available from Lubrizol Advanced Materials, Inc. under the Sensomer™ CT-250 and Sensomer™ CT-400 series or from Ashland Inc. under the ClearHance™ series.

[0101] It may be preferred that the cationic polymer is selected from the group consisting of cyclopolymers of alkyldiallylamine and cyclopolymers of dialkyldiallylammonium, such as (co)polydiallyldialkylammonium chloride, (co)polyamines, such as (co)polylysine, cationic (co)polyamino acids, such as cationized collagen, cationic cellulose polymers, and salts thereof.

[0102] It may also be preferred that the cationic polymer is selected from chitosan.

[0103] It may be more preferred that the cationic polymer is selected from the group consisting of polylysine, polyquaternium-4, polyquaternium-10, polyquaternium-24, polyquaternium-67, starch hydroxypropyltrimonium chloride, cassia hydroxypropyltrimonium chloride, chitosan, and mixtures thereof.

[0104] The amount of cationic polymer in the composition according to the invention may be greater than or equal to 0.01% by weight, preferably greater than or equal to 0.05% by weight, more preferably greater than or equal to 0.1% by weight, relative to the total weight of the composition.

[0105] The amount of cationic polymer in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, relative to the total weight of the composition.

[0106] The amount of cationic polymer in the composition according to the present invention can be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

[0107] (anionic polymer) The anionic polymer has a positive charge density. When the anionic polymer is a synthetic anionic polymer, the charge density of the anionic polymer may be 0.1 meq / g to 20 meq / g, preferably 1 to 15 meq / g, and more preferably 4 to 10 meq / g. When the anionic polymer is a natural anionic polymer, the average degree of substitution of the anionic polymer may be 0.1 to 3.0, preferably 0.2 to 2.7, and more preferably 0.3 to 2.5.

[0108] It may be preferred that the molecular weight of the anionic polymer is 300 or more, preferably 1,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, even more preferably 1,000,000 or more.

[0109] Unless otherwise defined in the description, "molecular weight" can mean number average molecular weight.

[0110] The anionic polymer may have at least one negatively charged moiety selected from the group consisting of sulfate groups, sulfate groups, sulfonic acid groups, sulfonate groups, phosphoric acid groups, phosphate groups, phosphonic acid groups, phosphonate groups, carboxylic acid groups, and carboxylate groups.

[0111] The anionic polymer may be a homopolymer or a copolymer. The term "copolymer" is understood to mean both copolymers obtained from two types of monomers and copolymers obtained from more than two types of monomers, for example terpolymers obtained from three types of monomers.

[0112] The anionic polymer can be selected from natural and synthetic anionic polymers.

[0113] The anionic polymer may comprise at least one hydrophobic chain.

[0114] Anionic polymers which may contain at least one hydrophobic chain can be obtained by copolymerizing a monomer (a) chosen from a carboxylic acid containing α,β-ethylenic unsaturation (monomer a′) and 2-acrylamido-2-methylpropanesulfonic acid (monomer a″) with a non-surface-active monomer containing ethylenic unsaturation other than (a) (b) and / or a monomer (c) containing ethylenic unsaturation obtained by reacting an acrylic monomer containing α,β-monoethylenic unsaturation or an isocyanate monomer containing monoethylenic unsaturation with a monovalent nonionic amphiphilic component or a primary or secondary fatty amine.

[0115] Thus, anionic polymers having at least one hydrophobic chain can be obtained by one of two synthetic routes: by copolymerization of the monomers (a') and (c), or (a'), (b) and (c), or (a'') and (c), or (a''), (b) and (c), or by modifying (e.g. esterifying or amidating) the monomer (a'), or a copolymer formed from the monomers (a') and (b), or (a'') and (b), with a monovalent non-ionic amphiphilic compound or a primary or secondary fatty amine.

[0116] As 2-acrylamido-2-methylpropanesulfonic acid copolymers, mention may be made in particular of those disclosed in the article "Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules, 2000, Vol. 33, No. 10, pp. 3694-3704" and in the applications EP-A-0750899 and EP-A-1069172.

[0117] The carboxylic acid containing α,β-monoethylenic unsaturation constituting the monomer (a′) can be chosen from a large number of acids, in particular from acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and is preferably acrylic acid or methacrylic acid.

[0118] The copolymer may contain a monomer (b) containing monoethylenic unsaturation without surfactant properties. Preferred monomers are those which, when homopolymerized, give water-insoluble polymers. These can be selected, for example, from acrylic acid and alkyl methacrylates (C1-C4), such as methyl acrylate, ethyl acrylate, butyl acrylate, or the corresponding methacrylates. More particularly preferred monomers are methyl acrylate and ethyl acrylate. Other monomers which may be used are, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and vinylidene chloride. Nonreactive monomers are preferred, and these monomers are those in which a single ethylenic group is the only group reactive under the polymerization conditions. However, monomers containing a group which reacts under the action of heat, such as hydroxyethyl acrylate, can optionally be used.

[0119] Monomer (c) is obtained by reacting an acrylic monomer containing α,β-monoethylenic unsaturation, such as (a), or an isocyanate monomer containing monoethylenic unsaturation, with a monovalent nonionic amphiphilic compound or a primary or secondary fatty amine.

[0120] The monovalent nonionic amphiphilic compounds or primary or secondary fatty amines used to produce the nonionic monomer (c) are well known. The monovalent nonionic amphiphilic compounds are generally alkoxylated hydrophobic compounds containing alkylene oxides that form the hydrophilic portion of the molecule. The hydrophobic compounds are generally composed of aliphatic alcohols or alkylphenols, in which a carbonaceous chain containing at least 6 carbon atoms constitutes the hydrophobic portion of the amphiphilic compound.

[0121] Preferred monovalent nonionic amphiphilic compounds are compounds having the following formula (V): R-(OCH2CHR') m -(OCH2CH2) n -OH (V) wherein R is selected from alkyl or alkylene groups containing 6 to 30 carbon atoms and alkylaryl groups having alkyl groups containing 8 to 30 carbon atoms; R' is selected from alkyl groups containing 1 to 4 carbon atoms; n is an average number ranging from approximately 1 to 150; and m is an average number ranging from approximately 0 to 50, with the proviso that n is at least as large as m.

[0122] Preferably, in the compounds of formula (V), the R group is an alkyl group containing 12 to 26 carbon atoms and the alkyl group is a C8 to C 13 wherein R′ is a methyl group, m=0, and n=1-25.

[0123] Preferred primary and secondary fatty amines are composed of one or two alkyl chains containing from 6 to 30 carbon atoms.

[0124] The monomers used to form the nonionic urethane monomer (c) can be selected from a wide variety of compounds. Any compound containing copolymerizable unsaturation, such as acrylic, methacrylic, or allylic unsaturation, can be used. Monomer (c) can be derived, in particular, from isocyanates containing monoethylenic unsaturation, such as, in particular, α,α-dimethyl-m-isopropenylbenzyl isocyanate.

[0125] Monomer (c) is in particular an oxyethylenated (1 to 50EO) C6 to C 30 Acrylates, methacrylates or itaconates of fatty alcohols, such as steareth-20 methacrylate, oxyethylenated (25EO) behenyl methacrylate, oxyethylenated (20EO) monocetyl itaconate, oxyethylenated (20EO) monostearyl itaconate or polyoxyethylenated (25EO) C 12 ~C 24 From alcohol-modified acrylates and oxyethylenated (1-50EO) C6-C 30It can be chosen from the dimethyl-m-isopropenylbenzyl isocyanates of fatty alcohols, such as the dimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenyl alcohol.

[0126] According to a particular embodiment of the present invention, the anionic polymer is selected from an acrylic terpolymer obtained from (a) a carboxylic acid containing α,β-ethylenic unsaturation, (b) a non-surface-active monomer containing ethylenic unsaturation other than (a), and (c) a nonionic urethane monomer which is the reaction product of a monovalent nonionic amphiphilic compound with an isocyanate containing monoethylenic unsaturation.

[0127] Examples of anionic polymers comprising at least one hydrophobic chain include, in particular, acrylic acid / ethyl acrylate / alkyl acrylate terpolymers, such as the product sold as a 30% aqueous dispersion under the name Acusol 823 by Rohm & Haas; acrylates / steareth-20 methacrylate copolymers, such as the product sold as an aqueous emulsion under the name Aculyn 22 by Rohm & Haas; (meth)acrylic acid / ethyl acrylate / oxyethylated (25EO) behenyl methacrylate terpolymers, such as the product sold as an aqueous emulsion under the name Aculyn 28 by Rohm & Haas; acrylic acid / oxyethylated (20EO) monocetyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch; acrylic acid / oxyethylated (20EO) monostearyl itaconate copolymers, such as the product sold as a 30% aqueous dispersion under the name Structure 3001 by National Starch. Product sold as a 30% aqueous dispersion in 2001; Acrylate / Polyoxyethylenated (25EO)C 12 ~C 24Mention may be made of copolymers of alcohol-modified acrylates, such as the 30-32% copolymer latex sold under the name Synthalen W2000 by the company 3V SA; or the terpolymer of methacrylic acid / methyl acrylate / ethoxylated behenyl alcohol with dimethyl-meta-isopropenylbenzyl isocyanate, such as the product disclosed in document EP-A-0 173 109 as a 24% aqueous dispersion containing 40 ethylene oxide groups.

[0128] The anionic polymer may also be polyester-5, such as the product sold by Eastman Chemical Company under the name Eastman AQ™ 55S Polymer, which has the following chemical formula:

[0129] [ka]

[0130] (A: dicarboxylic acid moiety G: glycol moiety SO3 - Na + : Sodium sulfo group OH: hydroxyl group)

[0131] It may be preferred that the anionic polymer is selected from the group consisting of polysaccharides such as alginic acid, hyaluronic acid and cellulose polymers (e.g. carboxymethylcellulose), anionic (co)polyamino acids such as (co)polyglutamic acid, (co)poly(meth)acrylic acid, (co)polyamine acid, (co)polystyrenesulfonate, (co)poly(vinylsulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acid, (co)polyfumaric acid, maleic acid (co)polymers, and salts thereof.

[0132] The maleic acid copolymer may comprise one or more maleic acid comonomers and one or more comonomers selected from vinyl acetate, vinyl alcohol, vinyl pyrrolidone, olefins containing from 2 to 20 carbon atoms, and styrene.

[0133] Thus, "maleic acid copolymer" is understood to mean any polymer obtained by copolymerization of one or more maleic acid comonomers with one or more comonomers chosen from vinyl acetate, vinyl alcohol, vinylpyrrolidone, olefins containing 2 to 20 carbon atoms, such as octadecene, ethylene, isobutylene, diisobutylene or isooctylene, and styrene, the maleic acid comonomers being optionally partially or completely hydrolyzed. Preferably, hydrophilic polymers are used, i.e. polymers with a water solubility of 2 g / l or more.

[0134] In an advantageous embodiment of the invention, the maleic acid copolymer may have a mole fraction of maleic acid units between 0.1 and 1, more preferably between 0.4 and 0.9.

[0135] The weight average molar mass of the maleic acid copolymers can be between 1,000 and 500,000, preferably between 1,000 and 50,000.

[0136] It is preferred that the maleic acid copolymer is a styrene / maleic acid copolymer, more preferably sodium styrene / maleic acid copolymer.

[0137] Preferably, a copolymer of styrene and maleic acid in a 50 / 50 ratio is used.

[0138] For example, a styrene / maleic acid (50 / 50) copolymer in the form of its ammonium salt at 30% in water sold by Cray Valley under the reference SMA1000H®, or a styrene / maleic acid (50 / 50) copolymer in the form of its sodium salt at 40% in water sold by Cray Valley under the reference SMA1000HNa®, can be used.

[0139] The use of styrene / maleic acid copolymers, such as sodium styrene / maleic acid copolymer, can improve the wettability of films prepared with compositions according to the present invention.

[0140] According to one embodiment of the present invention, the anionic polymer is preferably chosen from hyaluronic acid and its derivatives.

[0141] Hyaluronic acid can be represented by the following chemical formula:

[0142] [ka]

[0143] In the context of the present invention, the term "hyaluronic acid" specifically encompasses the basic unit of hyaluronic acid of the formula:

[0144] [ka]

[0145] It is the smallest part of hyaluronic acid, containing a disaccharide dimer, i.e., D-glucuronic acid and N-acetylglucosamine.

[0146] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes linear polymers comprising the above polymer units linked together in a chain via alternating β(1,4) and β(1,3) glycosidic bonds, with a molecular weight (MW) that can range between 380 and 13,000,000 daltons, which depends primarily on the source from which the hyaluronic acid is obtained and / or the preparation method.

[0147] The term "hyaluronic acid and its derivatives" in the context of the present invention also includes hyaluronic acid salts, which may include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

[0148] In nature, hyaluronic acid is found in the percellular gel in the matrix of connective tissues of vertebrate organs, such as the dermis and epithelial tissues, particularly in the epidermis, in the synovial fluid of joints, in the vitreous humor, in the human umbilical cord, and in the crest process.

[0149] Therefore, the term "hyaluronic acid and its derivatives" includes all fractions or subunits of hyaluronic acid, especially those having molecular weights within the range of molecular weights envisaged above.

[0150] In the context of the present invention, it is preferred to use hyaluronic acid fractions that do not have inflammatory activity.

[0151] As an example of various hyaluronic acid degradation processes, reference may be made to the article "Hyaluronan fragments: an information-rich system", R. Stern et al., European Journal of Cell Biology 58 (2006) pp. 699-715, which reviews the enumerated biological activities of hyaluronic acid according to its molecular weight.

[0152] According to a preferred embodiment of the present invention, the hyaluronic acid fraction suitable for use in the present invention has a molecular weight of between 50,000 and 5,000,000, in particular between 100,000 and 5,000,000, and especially between 400,000 and 5,000,000 Da, in which case the term used is high molecular weight hyaluronic acid.

[0153] Alternatively, hyaluronic acid fractions that may also be suitable for use within the present invention have a molecular weight between 50,000 and 400,000 Da, in which case the term used is intermediate molecular weight hyaluronic acid.

[0154] Additionally or alternatively, hyaluronic acid fractions that may be suitable for use within the present invention have a molecular weight of less than 50,000 Da, in which case the term used is low molecular weight hyaluronic acid.

[0155] Finally, the term "hyaluronic acid and its derivatives" also includes hyaluronic acid esters, in particular those in which all or part of the carboxylic acid groups of the acid function are esterified with oxyethylenated alkyls or alcohols containing 1 to 20 carbon atoms, in particular those in which the degree of substitution of the hyaluronic acid at the level of D-glucuronic acid ranges from 0.5 to 50%.

[0156] Mention may in particular be made of the methyl, ethyl, n-propyl, n-pentyl, benzyl and dodecyl esters of hyaluronic acid, such esters being described, in particular, by D. Campoccia et al., "Semisynthetic resorbable materials from hyaluronan esterification", Biomaterials 19 (1998), pp. 2101-2127.

[0157] The hyaluronic acid derivative can be, for example, acetylated hyaluronic acid or a salt thereof.

[0158] The molecular weights given above are also valid for hyaluronic acid esters.

[0159] Specifically, hyaluronic acid is sold by Hyactive under the trade name CPN (MW: 10-150 kDa) and by Soliance under the trade name Cristalhyal (MW: 1.1 × 10 6 ), supplied by Bioland under the name Nutra HA (MW: 820000 Da), by Bioland under the name Nutra AF (MW: 69000 Da), by Bioland under the name Oligo HA (MW: 6100 Da), or else by Vam Farmacos Metica under the name D Factor (MW: 380 Da).

[0160] The amount of anionic polymer in the composition according to the invention may be greater than or equal to 0.01% by weight, preferably greater than or equal to 0.05% by weight, more preferably greater than or equal to 0.1% by weight relative to the total weight of the composition.

[0161] The amount of anionic polymer in the composition according to the invention may be up to 15% by weight, preferably up to 10% by weight, more preferably up to 5% by weight relative to the total weight of the composition.

[0162] The amount of anionic polymer in the composition according to the invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, relative to the total weight of the composition.

[0163] (Non-polymeric acids with two or more acid dissociation constants) The composition according to the present invention may contain at least one non-polymeric acid or salt thereof having two or more pKa values, i.e., at least one non-polymeric acid or salt thereof having two or more acid dissociation constants. pKa values ​​(acid dissociation constants) are well known to those skilled in the art and should be determined at a certain temperature, for example, 25°C.

[0164] A non-polymeric acid or salt thereof having two or more pKa values ​​can be incorporated into the (a) particles. The non-polymeric acid having two or more pKa values ​​can function as a crosslinker for the anionic polymer and / or the amphoteric polymer.

[0165] The term "non-polymeric" as used herein means that the acid is not obtained by polymerizing two or more monomers, and therefore does not correspond to acids obtained by polymerizing two or more monomers, such as polycarboxylic acids.

[0166] The molecular weight of the non-polymeric acid or salt thereof having two or more pKa values ​​is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

[0167] There is no limitation on the type of non-polymeric acid having two or more pKa values ​​or its salt. Two or more different types of non-polymeric acids having two or more pKa values ​​or their salts may be used in combination. Therefore, a single type of non-polymeric acid having two or more pKa values ​​or its salt, or a combination of different types of non-polymeric acids having two or more pKa values ​​or their salts, may be used.

[0168] The term "salt" as used herein refers to a salt formed by adding a suitable base to a non-polymeric acid having two or more pKa values, which can be obtained by reacting a non-polymeric acid having two or more pKa values ​​with a base according to a method known to those skilled in the art. Examples of the salt include metal salts, such as salts with alkali metals such as Na and K, salts with alkaline earth metals such as Mg and Ca, and ammonium salts.

[0169] The non-polymeric acid or salt thereof having two or more pKa values ​​may be an organic acid or salt thereof, preferably a hydrophilic or water-soluble organic acid or salt thereof.

[0170] The non-polymeric acid having two or more pKa values ​​can have at least two acid groups selected from the group consisting of carboxylic acid groups, sulfate groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, phenolic hydroxyl groups, and mixtures thereof.

[0171] A non-polymeric acid having two or more pKa values ​​may be a non-polymeric polyacid.

[0172] The non-polymeric acid having two or more pKa values ​​can be selected from the group consisting of dicarboxylic acids, disulfonic acids, and diphosphonic acids, and mixtures thereof.

[0173] Non-polymeric acids or salts thereof having two or more pKa values ​​include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid, citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and salts thereof; aspartic acid, glutamic acid, and salts thereof; terephthalylidene dicamphorsulfonic acid, and salts thereof (Mexoryl SX), Benzophenone-9; Phytic Acid and Its Salts; Red No. 2 (Amaranth), Red No. 102 (New Coccine), Yellow No. 5 (Tartrazine), Yellow No. 6 (Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF), Blue No. 2 (Indigo Carmine), Red No. 201 (Lithol Rubin B), Red No. 202 (Lithol Rubin BCA), Red No. 204 (Lake Red CBA), Red No. 206 (Lithol Red CA), Red No. 207 (Lithol Red BA), Red No. 208 (Lithol Red SR), Red No. 219 (Brilliant Lake Red R), Red No. 220 (Deep Maroon), Red No. 227 (Fast Acid Magenta), Yellow No. 203 (Quinoline Yellow W) S), Green No. 201 (Alizanin Cyanine Green F), Green No. 204 (Pyranine Concentrate), Green No. 205 (Light Green SF Yellow), Blue No. 203 (Patent Blue CA), Blue No. 205 (Alphazurine FG), Red No. 401 (Violamin R), Red No. 405 (Permanent Red F5R), Red No. 502 (Ponceau 3R), Red No. 503 (Ponceau R), Red No. 504 (Ponceau SX), Green No. 401 (Naphthol Green B), Green No. 402 (Guinea Green B) and Black No. 401 (Naphthol Blue Black); folic acid, ascorbic acid, erythorbic acid, and salts thereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizin and salts thereof; and mixtures thereof.

[0174] It may be preferred that the non-polymeric acid or salt thereof having two or more pKa values ​​is selected from the group consisting of terephthalylidene dicamphorsulfonic acid and its salts (Megizolil SX), Yellow No. 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and their salts, and mixtures thereof.

[0175] The amount of the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, based on the total weight of the composition.

[0176] The amount of non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition.

[0177] The amount of the non-polymeric acid or salt thereof having two or more pKa values ​​in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0178] [Filler] The composition according to the present invention comprises (b) at least one filler. Two or more fillers may be used in combination. Thus, a single type of filler or a combination of different types of fillers may be used.

[0179] The term "filler" should be understood to mean colorless or white, inorganic or synthetic particles that are insoluble in the liquid components that may be present in the composition according to the invention, whatever the temperature at which the composition is prepared.

[0180] (b) Fillers may be inorganic or organic, may have any crystalline form (e.g., lamellar, cubic, hexagonal, orthorhombic, etc.), and may be spherical or oval in shape. Examples include, but are not limited to, talc, mica, silica, silica silylate, kaolin, sericite, calcined talc, calcined mica, calcined sericite, synthetic mica, bismuth oxychloride, barium sulfate, boron nitride, calcium carbonate, magnesium carbonate, magnesium bicarbonate, and hydroxyapatite, powders formed from polyamide (Nylon®), poly-β-alanine and polyethylene, powders formed from polyurethane, powders formed from tetrafluoroethylene polymer (Teflon®), lauryl lysine, starch, hollow polymeric microspheres, such as hollow microspheres of poly(vinylidene chloride) / acrylonitrile, such as Expancel® (Nobel Industrie), or hollow microspheres of acrylic acid copolymers, silicone resin microbeads (e.g., Tospearls® from Toshiba), particles formed from polyorganosiloxane elastomers, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, hollow silica microspheres, glass or ceramic microcapsules, or metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, for example 12 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate.

[0181] In the present invention, examples of fillers include metal oxides, preferably titanium oxide, zinc oxide, and mixtures thereof.

[0182] Fillers suitable for the present invention may for example be fillers with an average particle size of less than 100 μm, in particular between 1 and 50 μm, for example between 4 and 20 μm.

[0183] (b) The filler can be selected from hydrophilic or hydrophobic oil absorbing powders.

[0184] Hydrophilic or hydrophobic oil-absorbing powders are capable of absorbing (and / or adsorbing) oil or liquid fatty substances, such as sebum (from the skin).

[0185] The hydrophilic or hydrophobic oil absorbing powder may comprise porous or hollow particles, in particular porous or hollow spherical particles.

[0186] [Hydrophilic oil-absorbing powder] For the purposes of the present invention, the term "hydrophilic" oil-absorbing powder means that the powder (or particles) are individually dispersed in water so that no agglomerates are formed.

[0187] The hydrophilic oil-absorbing powder may have an oil absorption capacity of 100 ml / 100 g or more, preferably 150 ml / 100 g or more, and more preferably 200 ml / 100 g or more.

[0188] The amount of oil absorbed (and / or adsorbed) by a hydrophilic oil-absorbing powder can be characterized by measuring the wetting point according to the method described below. The oil absorption capacity measured at the wetting point, denoted Wp, corresponds to the amount of oil that needs to be added to 100 g of powder to obtain a homogeneous paste.

[0189] The amount of oil absorbed (and / or adsorbed) can be measured according to the method for determining the oil absorption of powders described in NF Standard T 30-022. This corresponds to the amount of oil absorbed / adsorbed onto the available surface of the powder by measuring the wetting point.

[0190] An amount of powder m = 2 g is placed on a glass plate, and then oil (such as ester oil and silicone oil) is added dropwise. After adding 4-5 drops of oil to the powder, it is mixed using a spatula, and the addition of oil is continued until an agglomerate of oil and powder is formed. At this point, the oil is added drop by drop, and then the mixture is ground with the spatula. When a firm, smooth paste is obtained, the addition of oil is stopped. This paste should be able to be spread on the glass plate without cracking or forming lumps. The volume Vs (expressed in ml) of the oil used is then noted. The oil absorption corresponds to the Vs / m ratio.

[0191] Alternatively, oil absorption capacity can be measured according to JIS-K6217-4.

[0192] The hydrophilic oil-absorbing powder may be either organic or inorganic.

[0193] The hydrophilic oil absorbing powder can be selected from cellulose, silica, silicates; perlite; magnesium carbonate; magnesium hydroxide; and derivatives thereof; and mixtures thereof.

[0194] According to one embodiment, the cellulose derivative may be chosen from cellulose esters and ethers.

[0195] The term "cellulose ester" as used hereinabove and hereinafter refers to a polymer consisting of an α(1-4) sequence of partially or completely esterified anhydroglucose rings, the esterification being obtained by reacting all or only a portion of the free hydroxyl functional groups of the anhydroglucose rings with a linear or branched carboxylic acid or carboxylic acid derivative (acid chloride or acid anhydride) containing 1 to 4 carbon atoms. Preferably, the cellulose ester is obtained by reacting a portion of the free hydroxyl functional groups of the rings with a carboxylic acid containing 1 to 4 carbon atoms. Advantageously, the cellulose ester is selected from cellulose acetate, cellulose propionate, cellulose butyrate, cellulose isobutyrate, cellulose acetobutyrate, and cellulose acetopropionate, and mixtures thereof.

[0196] The term "cellulose ether" refers to a polymer consisting of an α(1-4) sequence of partially etherified anhydroglucose rings, some of the free hydroxyl functions of said rings being replaced by -OR groups, where R is preferably a linear or branched alkyl group containing 1 to 4 carbon atoms. Thus, the cellulose ether is preferably selected from cellulose alkyl ethers having alkyl groups containing 1 to 4 carbon atoms, such as cellulose methyl, propyl, isopropyl, butyl and isobutyl ethers.

[0197] Cellulose and its derivatives that may be mentioned include, for example, the following spherical cellulose particles sold by Daito Kasei Kogyo Co., Ltd., Japan: Cellulobeads USF with a particle size of 4 μm (oil absorption capacity of 250 ml / 100 g) (porous cellulose).

[0198] Silica powders that may be mentioned include porous silica microspheres, in particular those sold under the names Sunsphere® H31 and Sunsphere® H51 by Asahi Glass Co., Ltd. (oil absorption equal to 150 ml / 100 g) and MSS-500-3H by Kobo; amorphous hollow silica particles, in particular those sold under the name Silica Shells by Kobo (oil absorption equal to 550 ml / 100 g); porous silica microspheres sold under the name Silysia 350 by Fuji Silysia Chemical Ltd. (oil absorption equal to 310 ml / 100 g); and the silica powder sold under the name Finesil X35 by Oriental Silycas (oil absorption equal to 380 ml / 100 g).

[0199] A silicate that may be mentioned in particular is the aluminum silicate sold under the name Kyowaad® 700PEL by Kyowa Chemical Industry Co., Ltd. (oil absorption equal to 195 ml / 100 g).

[0200] Perlite powders that may be mentioned in particular are the products sold under the names Optimat® 1430 OR and Optimat® 2550 OR by the company World Minerals (oil absorption equal to 240 ml / 100 g).

[0201] A magnesium carbonate powder that may be mentioned in particular is the product sold under the name Tipo Carbomagel® by the company Buschle & Lepper (oil absorption equal to 214 ml / 100 g).

[0202] A magnesium carbonate / hydroxide powder that may be mentioned in particular is the product mMgCO3-Mg(OH)2-nH2O (oil absorption equal to 250-310 ml / 100 g) sold under the name Mg Tube by Nittetsu Mining Co., Ltd.

[0203] The hydrophilic oil-absorbing powder preferably contains at least one selected from the group consisting of cellulose, silica, perlite, and mixtures thereof.

[0204] (Hydrophobic oil-absorbing powder) For the purposes of the present invention, the term "hydrophobic" oil-absorbing powder means that the powder (or particles) are individually dispersed in the oil so that no agglomerates are formed.

[0205] The hydrophobic oil-absorbing powder may have an oil absorption capacity of 100 ml / 100 g or more, preferably 150 ml / 100 g or more, and more preferably 200 ml / 100 g or more.

[0206] The amount of oil absorbed (and / or adsorbed) by the hydrophobic oil absorbing powder can be determined by the method described above.

[0207] The hydrophobic oil-absorbing powder may be organic or inorganic.

[0208] Organic hydrophobic oil-absorbing powder: The organic hydrophobic oil-absorbing powder can be selected from the group consisting of polyamide (especially nylon-6) powder, acrylic polymer powder, especially polymethyl methacrylate, polymethyl methacrylate / ethylene glycol dimethacrylate, polyallyl methacrylate / ethylene glycol dimethacrylate, or ethylene glycol dimethacrylate / lauryl methacrylate copolymer powder, and mixtures thereof. The above materials may be crosslinked.

[0209] The organic hydrophobic oil-absorbing powder may preferably be selected from powders of acrylic polymers, especially ethylene glycol dimethacrylate / lauryl methacrylate copolymers.

[0210] Examples of organic hydrophobic oil-absorbing powders include the fillers described below.

[0211] Acrylic polymer powders that may be mentioned include porous polymethyl methacrylate (INCI name methyl methacrylate crosspolymer), for example the spheres sold under the name Covabead LH85 by Sensient, porous polymethyl methacrylate / ethylene glycol dimethacrylate spheres sold under the name Microsponge 5640 by Cardinal Health Technologies (oil absorption equal to 155 ml / 100 g), ethylene glycol dimethacrylate / lauryl methacrylate crosslinked copolymer powders, in particular those sold under the name Polytrap® 6603 by Amcol Health & Beauty Solutions (oil absorption equal to 656 ml / 100 g), and acrylonitrile / methyl methacrylate / vinylidene chloride copolymer sold under the name Expancel 551DE40D42 by Akzo Novel (oil absorption equal to 1,040 ml / 100 g).

[0212] Polyamide powders that may be mentioned include nylon-6 powder, in particular the product sold under the name Pomp 610 by Ube Industries (oil absorption equal to 202 ml / 100 g).

[0213] Inorganic hydrophobic oil-absorbing powder: The inorganic hydrophobic oil absorbing powder may have at least one inorganic core and at least one hydrophobic coating.

[0214] The inorganic hydrophobic oil absorbing powder is preferably selected from hydrophobic silica, preferably hydrophobic silica aerogel, more preferably hydrophobic aerogel of silica silylate, and mixtures thereof.

[0215] The term "hydrophobic silica" is understood to mean any silica whose surface has been treated to make it hydrophobic.

[0216] Hydrophobic silica, especially silica silylate, may be based on silica aerogel, a porous material obtained by replacing the liquid component of silica gel with air (by drying).

[0217] They are generally synthesized by the sol-gel method in a liquid medium and then dried, usually by extraction with a supercritical fluid, the most commonly used being supercritical CO2. This type of drying makes it possible to avoid pore and material shrinkage. The sol-gel method and various drying procedures are described in detail in Brinker CJ and Scherer GW, Sol-Gel Science, New York, Academic Press, 1990.

[0218] Aerogels are highly porous materials. In this specification, silica aerogel generally refers to solid silica with a porous structure obtained by drying wet silica gel while maintaining the solid silica network, thereby replacing the media contained in the wet silica gel with air. Porosity is expressed as the amount of air contained in the apparent volume of the material, expressed as a volume percentage. The hydrophobic silica aerogel of the present invention can have a porosity of 60% or more, preferably 70% or more, and more preferably 80% or more.

[0219] Hydrophobic silica aerogel particles are 500 to 1,500 m 2 / g, preferably 600 to 1,200m 2 / g, more preferably 600 to 800m 2 Specific surface area (SW) per mass unit in the range / g, and / or The particle size may be expressed as a volume average diameter (D[0.5]) in the range of 1 to 1,500 μm, preferably 1 to 1,000 μm, more preferably 1 to 100 μm, particularly 1 to 30 μm, more preferably 5 to 25 μm, more preferably 5 to 20 μm, and even more preferably 5 to 15 μm.

[0220] The specific surface area per mass unit can be determined by a nitrogen absorption method known as the BET (Brunauer-Emmett-Teller) method, which is described in The Journal of the American Chemical Society, Vol. 60, p. 309, February 1938, and corresponds to International Standard ISO 5794 / 1 (Annex D). The BET specific surface area corresponds to the total specific surface area of ​​the particles under consideration.

[0221] The size of hydrophobic silica aerogel particles can be measured by static light scattering using a commercially available particle size analyzer, the Malvern MasterSizer 2000. Data are processed based on Mie scattering theory. This theory, which is rigorous for isotropic particles, allows the determination of "effective" particle sizes for non-spherical particles. This theory is described in detail in Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

[0222] The hydrophobic silica aerogel particles are advantageously 0.04 g / cm 3 ~0.10g / cm 3 , preferably 0.05 g / cm 3 ~0.08g / cm 3 It can exhibit a packing density (r) in the range of

[0223] In the context of the present invention, this density, known as packing density, can be evaluated according to the following protocol: Pour 40g of powder into a graduated cylinder; The graduated cylinder is then placed in a Stav 2003 apparatus manufactured by Stampf Volumeter; The graduated cylinder is subsequently subjected to a series of 2500 filling operations (this operation is repeated until the volume difference between two consecutive tests is less than 2%); The final volume Vf of the packed powder is then measured directly in the measuring cylinder. The packing density is determined by the ratio m / Vf (Vf is cm), which in this case is 40 / Vf. 3 where w is determined by g).

[0224] For the preparation of hydrophobic silica aerogel particles surface-modified by silylation, reference may be made to US Pat. No. 7,470,725.

[0225] In particular, hydrophobic silica aerogel particles that are surface-modified with trimethylsilyl groups are used.

[0226] Inorganic hydrophobic oil-absorbing powders that may be mentioned include polydimethylsiloxane-coated amorphous silica microspheres, in particular those sold under the names Sunsphere® H33 and Sunsphere® H53 (oil absorption equal to 400 ml / 100 g), precipitated silica powders surface-treated with inorganic waxes, for example precipitated silica treated with polyethylene waxes, in particular those sold under the name Acematt OR 412 by Evonik-Degussa (oil absorption equal to 398 ml / 100 g), and silica silylate sold under the name VM-2270 by Dow (oil absorption equal to 1,040 ml / 100 g).

[0227] As inorganic hydrophobic oil-absorbing powder, it is preferable to use silica silylate sold under the name VM-2270 by Dow, the particles of which have an average size in the range of 5 to 15 μm and a viscosity of 600 to 800 μm. 2 The specific surface area per mass unit in the range of / g is shown.

[0228] The hydrophobic silica aerogel particles can be characterized by the spherical shape of each particle. This spherical shape allows the hydrophobic silica aerogel particles to provide good smoothness to cosmetic compositions. The sphericity of the hydrophobic silica aerogel can be determined by the average circularity.

[0229] The spherical hydrophobic silica aerogel particles may have an average circularity of 0.8 or more, preferably 0.82 or more. The spherical hydrophobic silica aerogel may have an average circularity of less than 1, preferably 0.99 or less, more preferably 0.98 or less, even more preferably 0.97 or less, even more preferably 0.96 or less, and most preferably 0.95 or less.

[0230] The "average circularity" can be determined by image analysis. In particular, the "average circularity" can be the arithmetic mean of the circularities obtained by image analysis of scanning electron microscope (SEM) images of 2,000 or more aerogel particles observed at 1,000 magnification by secondary electron detection using a scanning electron microscope (SEM).

[0231] The "circularity" of each aerogel particle is a value determined by the following formula: C=4πS / L 2 [where C represents circularity, S represents the area (projected area) of the aerogel particle in the image, and L represents the perimeter (outer perimeter) of the aerogel particle in the image]. As the average circularity approaches 1, the shape of each particle becomes more spherical.

[0232] The hydrophobic silica aerogel particles that can be used according to the present invention are preferably of the silylated silica type (INCI name: silica silylate).Preferably, the hydrophobic silica aerogel particles may be those described in JP-A-2014-088307, JP-A-2014-218433, or JP-A-2018-177620.

[0233] It is preferable to use a hydrophobic aerogel of silica silylate as the inorganic hydrophobic oil-absorbing powder.

[0234] The hydrophobicity of the silica silylate aerogel is determined by adding a hydrophobizing agent having the following formula present on the surface of the silica: ≡Si-OH (wherein the symbol "≡" represents the remaining valence of 3 on the Si atom) thereby converting the silanol group to the following formula: (≡Si-O-) (4-n) SiR n (wherein n is an integer of 1 to 3, each R is independently a hydrocarbyl group, and two or more Rs may be the same or different, and n is 2 or more). can be obtained by converting the group represented by the formula:

[0235] The hydrophobizing agent may be a silylating agent. Thus, according to a preferred embodiment, in the hydrophobic aerogel of silica silylate, the silica particles may be surface-modified by silylation. Examples of the silylating agent include a treatment agent having one of the following formulas (1) to (3):

[0236] Formula (1): R n Six (4-n) [wherein n represents an integer of 1 to 3, R represents a hydrocarbyl group, X represents a group that can be eliminated from the molecule by cleaving the bond to the Si atom during reaction with a compound having a hydroxyl group (i.e., a leaving group), each R may be different, where n is 2 or more, and each X may be different, where n is 2 or less].

[0237] Formula (2):

[0238] [ka]

[0239] [In the formula, R 1 represents an alkylene group, and R 2 and R 3 each independently represents a hydrocarbyl group; R 4 and R 5 independently represent a hydrogen atom or a hydrocarbyl group.

[0240] Formula (3):

[0241] [ka]

[0242] [In the formula, R 6 and R 7 each independently represents a hydrocarbyl group, m represents an integer of 3 to 6, and R 6 If there are two or more R 6 may be different, and R 7 If there are two or more R 7 may be different].

[0243] In the above formula (1), R is a hydrocarbyl group, preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a hydrocarbyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

[0244] Examples of the leaving group represented by X include halogen atoms such as chlorine and bromine, alkoxy groups such as methoxy and ethoxy, and groups represented by -NH-SiR3 (wherein R is defined as R in formula (1)).

[0245] Specific examples of the hydrophobizing agent represented by the above formula (1) include chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, and hexamethyldisilazane.

[0246] Most preferably, in view of favorable reactivity, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane, and / or hexamethyldisilazane may be used.

[0247] The number of bonds between the Si atom and the silanol groups on the silica backbone varies depending on the number of leaving groups X (4-n). For example, when n is 2, the following bonds are formed: (≡Si-O-)2SiR2

[0248] When n is 3, the following combination occurs: ≡Si-O-SiR3

[0249] In this way, the silanol groups can be silylated and thereby hydrophobized.

[0250] In the above formula (2), R 1 may be an alkylene group, preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 2 to 3 carbon atoms.

[0251] In the above formula (2), R 2 and R 3 are independently hydrocarbyl groups, and the same preferred groups as those of R in formula (1) can be mentioned. 4represents a hydrogen atom or a hydrocarbyl group, and when it is a hydrocarbyl group, the same preferred groups as R in formula (1) can be mentioned. When silica gel is treated with a compound represented by formula (2) (cyclic silazane), the reaction with the silanol groups causes cleavage of the Si-N bond, and therefore the following bond is formed on the surface of the silica skeleton in the gel: (≡Si-O-)2SiR 2 R 3

[0252] In this way, the silanol groups can also be silylated with the cyclic silazane of formula (2) above, thereby achieving hydrophobization.

[0253] Specific examples of the cyclic silazane represented by the above formula (3) include hexamethylcyclotrisilazane and octamethylcyclotetrasilazane.

[0254] In the above formula (3), R 6 and R 7 are independently hydrocarbyl groups, and the same preferred groups as R in formula (2) can be mentioned. m represents an integer of 3 to 6. When silica gel is treated with a compound (cyclic siloxane) represented by formula (3), the following bonds are formed on the surface of the silica skeleton in the gel: (≡Si-O-)2SiR 6 R 7

[0255] In this way, the silanol groups can also be silylated with the cyclic siloxane of formula (3) above, thereby achieving hydrophobicity.

[0256] Specific examples of the cyclic siloxane represented by the above formula (3) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0257] Silica silylate hydrophobic aerogels can be prepared by producing a silica sol, converting the sol to a gel, aging the gel, washing the aged gel, replacing the water in the washed gel with a solvent, treating the gel with a hydrophobizing agent, and drying the hydrophobized silica.

[0258] The specific surface area of ​​the silica silylate hydrophobic aerogel determined by the BET method is 200 m 2 / g or more, preferably 400m 2 / g or more, more preferably 500m 2 / g or more and 1200m 2 / g or less, preferably 1000m 2 / g or less, more preferably 800m 2 / g or less.

[0259] The pore volume of the silica silylate hydrophobic aerogel, as determined by the BJH method, can be 1 ml / g or more, preferably 2 ml / g or more, more preferably 3 ml / g or more, and 10 ml / g or less, preferably 8 ml / g or less, more preferably 7 ml / g or less.The peak pore radius of the silica silylate hydrophobic aerogel, as determined by the BJH method, can be 5 nm or more, preferably 10 nm or more, more preferably 12 nm or more, and 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less.

[0260] "Pore volume determined by the BJH method" refers to the pore volume derived from pores with pore radii of 1 nm to 100 nm, obtained by analyzing the nitrogen adsorption isotherm using the BJH method (Barrett, EP; Joyner, LG; Halenda, PP, J. Am. Chem. Soc. 73, 373 (1951)) in the same manner as the "specific surface area determined by the BET method" described above. "Peak pore radius determined by the BJH method" refers to the pore radius value that produces a peak in a pore distribution curve (volume distribution curve) plotted on the horizontal axis against the vertical axis, which is the derivative of the cumulative pore volume with respect to the logarithm of the pore radius, obtained by analyzing the nitrogen adsorption isotherm using the BJH method in the same manner as described above.

[0261] The silica silylate hydrophobic aerogel may have an average particle size of 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and may have an average particle size of 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, as measured by image analysis.

[0262] The "average particle size" here can be measured by image analysis. In particular, the "average particle size" value is the arithmetic mean of the equivalent circular diameters, which can be obtained by image analysis of a scanning electron microscope (SEM) image of 2,000 or more aerogel particles observed at 1,000x magnification using secondary electron detection. The "equivalent circular diameter" of each aerogel particle is the diameter of a circle having an area equal to the area (projected area) of the aerogel particle in the image.

[0263] Preferably, the oil absorption capacity of the silica silylate hydrophobic aerogel, which can be measured at the wet point as described above, is 2 ml / g or more, preferably 3 ml / g or more, more preferably 4 ml / g or more, most preferably 5 ml / g or more, and can be 12 ml / g or less, preferably 10 ml / g or less, more preferably 8 ml / g or less, most preferably 7 ml / g or less.

[0264] The amount of (b) filler in the composition according to the present invention may be 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, relative to the total mass of the composition.

[0265] The amount of (b) filler in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, relative to the total weight of the composition.

[0266] The amount of the (b) filler in the composition according to the present invention may be 0.01% by mass to 15% by mass, preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass to 5% by mass, relative to the total mass of the composition.

[0267] [water] The composition according to the present invention comprises (c) water.

[0268] (c) The amount of water can be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, based on the total weight of the composition.

[0269] (c) The amount of water may be 95% by weight or less, preferably 90% by weight or less, and more preferably 85% by weight or less, based on the total weight of the composition.

[0270] The amount of (c) water can be 50% by mass to 95% by mass, preferably 60% by mass to 90% by mass, and more preferably 70% by mass to 85% by mass, relative to the total mass of the composition.

[0271] [pH] The pH of the composition according to the present invention may be 3-9, preferably 3.3-8.5, and more preferably 3.5-8.

[0272] At a pH between 3 and 9, the (a) particles can be very stable.

[0273] The pH of the composition according to the present invention can be adjusted by adding at least one alkaline agent and / or at least one acid other than a non-polymeric acid or its salt having two or more pKa values ​​and incorporating it into the (a) particles. The pH of the composition according to the present invention can also be adjusted by adding at least one buffering agent.

[0274] (Alkaline agent) The composition according to the present invention may contain at least one alkaline agent. Two or more alkaline agents may be used in combination. Thus, a single type of alkaline agent or a combination of different types of alkaline agents may be used.

[0275] The alkaline agent may be an inorganic alkaline agent, preferably selected from the group consisting of ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phosphates and monohydrogen phosphates, such as sodium phosphate or sodium monohydrogen phosphate.

[0276] Examples of inorganic alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Sodium hydroxide is preferred as the inorganic alkaline agent.

[0277] The alkaline agent may be an organic alkaline agent, which is preferably selected from the group consisting of monoamines and derivatives thereof, diamines and derivatives thereof, polyamines and derivatives thereof, basic amino acids and derivatives thereof, oligomers of basic amino acids and derivatives thereof, polymers of basic amino acids and derivatives thereof, urea and derivatives thereof, and guanidine and derivatives thereof.

[0278] Examples of organic alkaline agents include alkanolamines, such as mono-, di-, and tri-ethanolamine, and isopropanolamine; urea, guanidine, and their derivatives; basic amino acids, such as lysine, ornithine, or arginine; and diamines, such as those having the following structure:

[0279] [ka]

[0280] (wherein R represents alkylene, such as propylene, optionally substituted with hydroxyl or a C1-C4 alkyl group; and R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group, or a C1-C4 hydroxyalkyl group), and examples thereof include 1,3-propanediamine and its derivatives. Arginine, urea, and monoethanolamine are preferred.

[0281] The alkaline agent can be used in a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass, relative to the total mass of the composition, depending on its solubility.

[0282] (acid) The compositions according to the present invention may comprise at least one acid. Two or more acids may be used in combination. Thus, a single type of acid or a combination of different types of acids may be used.

[0283] The acid may be any inorganic or organic acid commonly used in cosmetics, preferably an inorganic acid. Monobasic and / or polybasic acids may be used. Monobasic acids such as citric acid, lactic acid, sulfuric acid, phosphoric acid, and hydrochloric acid (HCl) may be used. HCl is preferred.

[0284] Depending on its solubility, the acid can be used in a total amount of 0.01% by mass to 15% by mass, preferably 0.02% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass, relative to the total mass of the composition.

[0285] (buffering agent) The compositions according to the present invention may comprise at least one buffering agent. Two or more buffering agents may be used in combination. Thus, a single type of buffering agent or a combination of different types of buffering agents may be used.

[0286] Buffers can include acetate buffers (e.g., acetic acid plus sodium acetate), phosphate buffers (e.g., sodium dihydrogen phosphate plus disodium hydrogen phosphate), citrate buffers (e.g., citric acid plus sodium citrate), borate buffers (e.g., boric acid plus sodium borate), tartrate buffers (e.g., tartaric acid plus sodium tartrate dihydrate), Tris buffers (e.g., tris(hydroxymethyl)aminomethane), and Hepes buffer (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[0287] [oil] The composition according to the present invention may comprise at least one oil. When two or more (d) oils are used, they may be the same or different.

[0288] As used herein, "oil" refers to a fatty compound or substance in the form of a liquid or paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As oils, those commonly used in cosmetics can be used alone or in combination. These oils can be volatile or non-volatile.

[0289] The oil may be a hydrocarbon oil, a non-polar oil such as a silicone oil, a vegetable oil or an animal oil, and a polar oil such as an ester oil or an ether oil, or a mixture thereof.

[0290] The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

[0291] Examples of vegetable oils include apricot oil, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

[0292] Examples of animal oils include squalene and squalane.

[0293] Examples of synthetic oils include alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

[0294] The ester oil is preferably a saturated or unsaturated, linear or branched C1-C 26 Aliphatic mono- or polyacids and saturated or unsaturated linear or branched C1-C 26 It is a liquid ester of an aliphatic monohydric alcohol or polyhydric alcohol, and the total number of carbon atoms in the ester is 10 or more.

[0295] Preferably, in the case of esters of monohydric alcohols, at least one of the alcohol and acid from which the esters of the present invention are derived is branched.

[0296] Among the monoesters of monoacids and monohydric alcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

[0297] C4~C 22 Dicarboxylic or tricarboxylic acids and C1-C22 Esters with alcohols, and monocarboxylic, dicarboxylic or tricarboxylic acids with non-sugar C4-C 26 Esters with dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols can also be used.

[0298] Mention may in particular be made of: diethyl sebacate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate.

[0299] As ester oil, C6-C 30 , preferably C 12 ~C 22 Sugar esters and diesters of fatty acids can be used. It is recalled that the term "sugar" means an oxygen-containing hydrocarbon-based compound containing at least four carbon atoms, with or without aldehyde or ketone functional groups, and containing several alcohol functional groups. These sugars can be monosaccharides, oligosaccharides, or polysaccharides.

[0300] Examples of suitable sugars that may be mentioned are sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, as well as derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for example methylglucose.

[0301] Sugar esters of fatty acids are, in particular, those made by esterifying the aforementioned sugars with linear or branched, saturated or unsaturated C6-C 30, preferably C 12 ~C 22 They can be selected from the group comprising esters or mixtures of esters with fatty acids, which, when unsaturated, can have 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

[0302] The esters according to this variant can also be chosen from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

[0303] These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, coconut, stearate, linoleate, linolenate, caprate and arachidonic acid esters, or mixtures thereof, such as, inter alia, mixed esters of oleopalmitate, oleostearate and palmitostearate, and pentaerythrityl tetraethylhexanoate.

[0304] More particularly, monoesters and diesters are used, in particular the mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates of sucrose, glucose or methylglucose.

[0305] An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

[0306] Examples of preferred ester oils include diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate / 2-ethylhexyl caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, charcoal, and the like. Examples of suitable alkyl acrylates include dicaprylyl lauroyl sarcosinate, isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

[0307] Examples of artificial triglycerides include caprylic / caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, capric / caprylic triglyceride, and capric / caprylic / linolenic triglyceride.

[0308] Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; and mixtures thereof.

[0309] Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes containing at least one aryl group.

[0310] These silicone oils may also be organically modified. The organically modified silicones that may be used according to the present invention are silicone oils as defined above and which contain in their structure one or more organic functional groups linked via hydrocarbon-based groups.

[0311] Organopolysiloxanes are further defined in Walter Noll's Chemistry and Technology of Silicones, Academic Press, 1968. Organopolysiloxanes can be volatile or nonvolatile.

[0312] When they are volatile, the silicones are more particularly chosen from those having a boiling point between 60° C. and 260° C., and even more particularly chosen from: (i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms, such as octamethylcyclotetrasiloxane, sold in particular under the name Volatile Silicone® 7207 by Union Carbide or under the name Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane, sold in particular under the name Volatile Silicone® 7158 by Union Carbide or under the name Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane, sold under the name Silsoft 1217 by Momentive Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the following type, such as dimethylsiloxane / methylalkylsiloxane of the formula: for example Silicone Volatile® FZ 3109, sold by Union Carbide.

[0313] [ka]

[0314] Also included are mixtures of cyclic polydialkylsiloxanes and organosilicon compounds, such as a 50 / 50 mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol, and a mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane. (ii) Contains 2 to 9 silicon atoms and has a density of 5 × 10 at 25 °C -6 m 2 Linear, volatile polydialkylsiloxanes with a viscosity of less than 1 / s. An example is decamethyltetrasiloxane, sold in particular by Toray Silicone under the name SH 200. Silicones belonging to this class are also described in an article published by Todd & Byers in Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM Standard 445, Appendix C.

[0315] Non-volatile polydialkylsiloxanes may also be used, these being more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

[0316] Among these polydialkylsiloxanes, mention may be made, but is not limited to, the following commercial products: Silbione® oils of the 47 and 70 047 series or Mirasil® oils sold by the company Rhodia, such as 70 047 V 500 000 oil; - Mirasil® series oils sold by Rhodia; - 200 series oils from Dow Corning, e.g., with a viscosity of 60,000mm2 / s DC200; and - Viscasil® oils manufactured by General Electric and certain oils of the SF series manufactured by General Electric (SF 96, SF 18).

[0317] Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups, known under the name dimethiconol (CTFA), such as the 48 series oils from Rhodia.

[0318] Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes, such as phenylsilicone oils.

[0319] The phenylsilicone oil can be chosen from phenylsilicones of the formula:

[0320] [ka]

[0321] (In the formula, R1~R 10 are, independently of one another, saturated or unsaturated, linear, cyclic or branched C1-C 30 Hydrocarbon groups, preferably C1-C 12 a hydrocarbon group, more preferably a C1 to C6 hydrocarbon group, specifically a methyl, ethyl, propyl, or butyl group; m, n, p, and q are each independently an integer of 0 to 900, inclusive, preferably an integer of 0 to 500, inclusive, and more preferably an integer of 0 to 100, inclusive; However, the sum n+m+q is not 0.

[0322] Examples that may be mentioned include products sold under the following names: - Silbione® oils from the 70 641 series manufactured by Rhodia; - oils of the Rhodorsil® 70 633 and 763 series manufactured by Rhodia; - Dow Corning 556 Cosmetic Grade Fluid, an oil manufactured by Dow Corning; - PK series silicones manufactured by Bayer, for example product PK20; Certain oils of the SF series manufactured by General Electric, such as SF 1023, SF 1154, SF 1250, and SF 1265.

[0323] Phenyl silicone oils include phenyl trimethicone (R1 to R2 in the above formula). 10 is methyl, p, q, and n=0, and m=1).

[0324] The organically modified silicone fluids may in particular contain polyethyleneoxy and / or polypropyleneoxy groups, and thus mention may be made of silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd., and the oils Silwet® L722 and L77 from Union Carbide.

[0325] The hydrocarbon oil may be selected from: - Linear or branched, optionally cyclic C6-C 16 lower alkanes (examples that may be mentioned are hexane, undecane, dodecane, tridecane, and isoparaffins, such as isohexadecane, isododecane, and isodecane); and - linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum, polydecene and hydrogenated polyisobutenes, such as Parleam®, and squalane.

[0326] Preferred examples of hydrocarbon oils include linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g., liquid paraffin), paraffin, Vaseline or petrolatum, naphthalene, etc.; hydrogenated polyisobutene, isoeicosane, and decene / butene copolymers; and mixtures thereof.

[0327] The term "fatty" in fatty alcohol means containing a relatively large number of carbon atoms. Therefore, alcohols having 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 12 or more carbon atoms are included within the scope of fatty alcohol. Fatty alcohols may be saturated or unsaturated. Fatty alcohols may be linear or branched.

[0328] The fatty alcohol may have the structure R—OH, where R is selected from saturated and unsaturated, linear and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R is selected from C 12 ~C 20 Alkyl groups and C 12 ~C 20 R may be selected from alkenyl groups, which may or may not be substituted with at least one hydroxyl group.

[0329] Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

[0330] Preferably, the fatty alcohol is a saturated fatty alcohol.

[0331] Thus, fatty alcohols may be linear or branched, saturated or unsaturated, C6-C 30 Alcohols, preferably linear or branched, saturated C6-C 30 Alcohols, more preferably linear or branched, saturated C 12 ~C 20 You can choose from alcohol.

[0332] The term "saturated fatty alcohol" as used herein means an alcohol having a long aliphatic saturated carbon chain. A saturated fatty alcohol may be any linear or branched saturated C-C 30 Preferably, the alcohol is selected from linear or branched saturated C6-C6 fatty alcohols. 30 Among fatty alcohols, linear or branched saturated C 12 ~C 20 Fatty alcohols are preferably used. Any linear or branched saturated C 16 ~C 20 Fatty alcohols are more preferably used. 16 ~C 20 Fatty alcohols may even more preferably be used.

[0333] Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetearyl alcohol), and behenyl alcohol can be used as saturated fatty alcohols.

[0334] According to at least one embodiment, the fatty alcohols used in the compositions according to the invention are preferably chosen from octyldodecanol, hexyldecanol, and mixtures thereof.

[0335] According to the present invention, the (d) oil may be surrounded by a plurality of (a) particles, or the (d) oil may be present within the hollow of a capsule formed by the (a) particles. In other words, the (d) oil may be covered by the (a) particles, or the capsule formed by the (a) particles contains the (d) oil within the hollow of the capsule.

[0336] The (d) oil surrounded by the (a) particles or present in the hollow of the capsule formed by the (a) particles cannot directly contact keratinous materials such as skin. Therefore, even if the (d) oil has a sticky or oily feel when used, the composition according to the present invention is not considered to have a sticky or oily feel when used.

[0337] The amount of (d) oil in the composition according to the present invention may be 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total mass of the composition.

[0338] The amount of (d) oil in the composition according to the present invention may be 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the composition.

[0339] The amount of (d) oil in the composition according to the present invention may be 0.1% by mass to 50% by mass, preferably 0.5% by mass to 40% by mass, and more preferably 1% by mass to 30% by mass, relative to the total mass of the composition.

[0340] [Optional Additives] In addition to the above-mentioned components, the composition according to the present invention may contain components typically used in cosmetics, specifically surfactants (particularly nonionic surfactants) or emulsifiers, hydrophilic or lipophilic thickeners, organic volatile or nonvolatile solvents, hydrophilic or hydrophobic UV screening agents, (d) silicones and silicone derivatives other than oils, natural extracts derived from animals or plants, waxes, etc., within ranges that do not impair the effects of the present invention.

[0341] The composition according to the present invention may contain the above-mentioned optional additives in an amount of 0.01% to 50% by weight, preferably 0.05% to 30% by weight, more preferably 0.1% to 10% by weight, relative to the total weight of the composition.

[0342] [Composition] The composition according to the present invention may be intended to be used as a cosmetic composition. Therefore, the cosmetic composition according to the present invention may be intended to be applied to keratinous materials. In this specification, keratinous materials refer to materials containing keratin as a main component, and examples thereof include skin, scalp, nails, lips, hair, etc. Therefore, the cosmetic composition according to the present invention is preferably used in a beauty method for keratinous materials, particularly skin.

[0343] Therefore, the cosmetic composition according to the present invention may be a skin cosmetic composition, preferably a skin care composition or a skin make-up composition, more preferably a skin care composition.

[0344] The composition according to the present invention can be prepared by mixing the essential and optional ingredients described above according to any of the methods well known to those skilled in the art.

[0345] If necessary, the essential components or optional components may be heated, and thus heating can be carried out when mixing the essential components and optional components.

[0346] When the composition according to the present invention contains (d) oil, it may be in the form of an emulsion, an O / W emulsion, or a W / O emulsion. The composition according to the present invention is preferably in the form of an O / W emulsion, because it can impart a refreshing feeling due to (c) water forming its external phase.

[0347] [Coating] The composition according to the present invention can be used to easily prepare a coating: (a) the particles can aggregate and coalesce into a continuous coating;

[0348] The present invention therefore also relates to a method for preparing a film, preferably a cosmetic film, optionally having a thickness of more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, comprising: applying a composition according to the invention to a substrate, preferably a keratinous material, more preferably the skin; drying the composition; The present invention also relates to a method comprising:

[0349] There is no upper limit to the thickness of the coating. For example, the thickness of the coating may be 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.

[0350] The method for preparing a film that can be related to the present invention includes a step of applying the composition according to the present invention to a substrate, preferably a keratinous material, more preferably skin, and a step of drying the composition, so the method does not require any spin coating or spraying, and therefore even a relatively thick film can be easily prepared. Therefore, the method for preparing a film that can be related to the present invention can prepare a relatively thick film without using any special equipment such as a spin coater or a spray machine.

[0351] Although the film prepared by the above method is relatively thick, it can still be thin and transparent, and therefore may not be easily perceived. Therefore, the film can preferably be used as a cosmetic film.

[0352] If the substrate is not a keratinous material such as skin, the composition according to the present invention can be applied to a substrate made of any material other than keratin. The material of the non-keratinous substrate is not limited. Two or more materials may be used in combination. Therefore, a single type of material or a combination of different types of materials may be used. In any case, the substrate is preferably flexible or elastic.

[0353] If the substrate is not a keratin material, it is preferable that the substrate is water-soluble, since a film can be left behind by washing the substrate with water. Examples of water-soluble materials include poly(meth)acrylic acid, polyethylene glycol, polyacrylamide, polyvinyl alcohol (PVA), starch, cellulose acetate, etc. PVA is preferred.

[0354] When the non-keratin substrate is in the form of a sheet, it may have a thickness greater than that of the film prepared by the above method, in order to facilitate handling of the film attached to the substrate sheet. The thickness of the non-keratin substrate sheet is not limited, but may be 1 μm to 5 mm, preferably 10 μm to 1 mm, and more preferably 50 to 500 μm.

[0355] It is more preferable that the film prepared by the above method can be peeled off from the non-keratin substrate. The peeling method is not limited. Therefore, the film prepared by the above method may be peeled off from the non-keratin substrate, or may be peeled off by dissolving the substrate sheet in a solvent such as water.

[0356] Therefore, the present invention also provides (1) A film, preferably a decorative film, optionally having a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, applying a composition according to the invention to a substrate, preferably a keratinous material, more preferably the skin; drying the composition; a coating prepared by a method comprising: and (2) A film, preferably a decorative film, optionally having a thickness of preferably more than 0.1 μm, more preferably 1.5 μm or more, even more preferably 2 μm or more, at least one cationic polymer and at least one anionic polymer; and At least one non-polymeric acid or salt thereof having two or more pKa values, and Optionally, at least one oil Including, coating Also relates to.

[0357] The above descriptions regarding cationic and anionic polymers, and non-polymeric acids or salts thereof having two or more pKa values, and oils described above, are applicable to those in coatings (1) and (2) above.

[0358] The film thus obtained can be self-supporting. The term "self-supporting" as used herein means that the film can be in the form of a sheet and can be handled as an independent sheet without the aid of a substrate or support. Thus, the term "self-supporting" can have the same meaning as "self-supporting."

[0359] The coating is preferably hydrophobic.

[0360] The term "hydrophobic" as used herein means that the solubility of the polymer in water (preferably in a volume of 1 liter) at 20 to 40° C., preferably 25 to 40° C., more preferably 30 to 40° C., is less than 10% by mass, preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1% by mass, based on the total mass of the polymer. Most preferably, the polymer is not soluble in water.

[0361] When the film is hydrophobic, it can have water-resistant properties and therefore can remain on a keratinous material such as skin even when the surface of the keratinous material is wet, for example, by sweat or rain. Therefore, when the film provides a cosmetic effect, the cosmetic effect can last for a long time.

[0362] On the other hand, the above-mentioned film can be easily removed from keratinous materials such as skin under alkaline conditions of pH 8 to 12, preferably 9 to 11. Therefore, although the above-mentioned film is difficult to remove with water, it can be easily removed with soap that can create such alkaline conditions.

[0363] The coating may include a layer of at least one biocompatible and / or biodegradable polymer. Two or more biocompatible and / or biodegradable polymers may be used in combination. Thus, a single type of biocompatible and / or biodegradable polymer or a combination of different types of biocompatible and / or biodegradable polymers may be used.

[0364] The term "biocompatible" polymer as used herein means that the polymer does not have excessive interactions between the polymer and cells in the body, including the skin, and the polymer is not recognized as foreign by the body.

[0365] The term "biodegradable" polymer as used herein means that the polymer can be broken down or degraded in vivo, for example, by the organism's own metabolism or the metabolism of microorganisms that may be present in the organism. Biodegradable polymers can also be broken down by hydrolysis.

[0366] When the coating comprises a biocompatible and / or biodegradable polymer, it is less or not irritating to the skin and does not cause any rashes. In addition, the use of a biocompatible and / or biodegradable polymer allows the coating to adhere well to the skin.

[0367] Said film can be used for keratinous material, preferably skin, especially face cosmetic treatment.Said film can be any shape or form.For example, it can be used as a full face mask sheet, or a patch for a part of face, such as cheek, nose and around eyes.

[0368] When the above-mentioned film contains at least one hydrophilic or water-soluble UV filter, the film can provide a UV shielding effect derived from the hydrophilic or water-soluble UV filter. Usually, the hydrophilic or water-soluble UV filter can be removed from the surface of a keratin substrate such as skin by water such as sweat and rain. However, since the hydrophilic or water-soluble UV filter is contained in the above-mentioned film, it is difficult to remove the hydrophilic or water-soluble UV filter with water, thereby providing a long-lasting UV shielding effect.

[0369] [Cosmetic methods and use] The present invention also provides A cosmetic method for keratinous materials such as skin, comprising: applying a composition according to the invention to keratinous materials; drying the composition to form a cosmetic film on the keratinous material; a method comprising: and Use of the composition according to the invention for preparing a cosmetic film on a keratinous material such as the skin Also relates to.

[0370] By cosmetic method in this specification is meant a non-therapeutic cosmetic method for caring for and / or making up the surface of keratinous materials such as the skin.

[0371] In both the above method and use, the above cosmetic film is resistant to water with a pH of 7 or less, and is removable with water with a pH of above 7, preferably 8 or more, more preferably 9 or more.

[0372] In other words, the decorative film may be water-resistant under neutral or acidic conditions, such as a pH of 7 or less, preferably in the range of 6 to 7, more preferably in the range of 5 to 7, but may be removed under alkaline conditions, such as a pH of more than 7, preferably 8 or more, more preferably 9 or more. The upper limit of the pH is preferably 13, more preferably 12, and even more preferably 11.

[0373] Accordingly, the cosmetic film can be water-resistant and therefore can remain on a keratinous material such as skin even when the surface of the keratinous material is wet, for example, by sweat or rain. Meanwhile, the cosmetic film can be easily removed from a keratinous material such as skin under alkaline conditions. Therefore, the cosmetic film is difficult to remove with water, but can be easily removed with a soap that can create alkaline conditions.

[0374] When the cosmetic film comprises a UV filter, which may be present in the composition according to the present invention, the cosmetic film can protect keratinous materials such as skin from UV rays, thereby reducing skin darkening, improving skin tone and evenness, and / or treating skin aging.

[0375] Furthermore, the above-mentioned cosmetic film may have cosmetic effects such as absorbing or adsorbing malodors and / or protecting keratinous materials from dirt or pollutants, due to the properties of the polyion complex particles in the cosmetic film, even if the cosmetic film does not contain any cosmetic active ingredients.

[0376] In addition, the cosmetic film can instantly change or modify the appearance of the skin by changing the light reflection on the skin, even if the cosmetic film does not contain any cosmetic active ingredients. Thus, the cosmetic film may be able to hide skin imperfections such as pores or wrinkles. Furthermore, the cosmetic film can instantly change or modify the feel of the skin by changing the surface roughness on the skin, etc. Furthermore, the cosmetic film can instantly protect the skin from environmental stresses, such as pollutants, impurities, etc., by covering the surface of the skin and shielding the skin as a barrier.

[0377] The cosmetic benefits can be adjusted or controlled by varying the chemical composition, thickness and / or surface roughness of the cosmetic film.

[0378] When the cosmetic film includes at least one additional cosmetic active ingredient other than (d) oil, the cosmetic film can have a cosmetic effect brought about by the additional cosmetic active ingredient. For example, when the cosmetic film includes at least one cosmetic active ingredient selected from an anti-aging agent, a sebum suppressant, a deodorant, an antiperspirant, a whitening agent, and a mixture thereof, the cosmetic film can treat skin aging, absorb sebum on the skin, control odor on the skin, control sweating on the skin, and / or whiten the skin.

[0379] After application to the skin, it is also possible to apply a makeup cosmetic composition to the cosmetic film or sheet. [Example]

[0380] The present invention will now be illustrated in a more detailed manner by examples, which should not, however, be construed as limiting the scope of the present invention.

[0381] (Examples 1 to 11 and Comparative Examples 1 to 13) [Preparation] Each of the compositions according to Examples 1 to 11 and Comparative Examples 1 to 13 was prepared by mixing the components shown in Tables 1 to 5 according to the following steps 1 to 7.

[0382] 1. Phase A ingredients were mixed and homogenized at 75°C + / - 5°C to obtain Phase A mixture. 2. The ingredients of Phase B were added to the mixture of Phase A and homogenized at 75°C + / - 5°C to obtain a mixture of Phases A and B. 3. The ingredients of Phase C were added to the mixture of Phases A and B obtained in step 2 and homogenized at 75°C + / - 5°C to obtain a mixture of Phases A, B and C. 4. Add the ingredients of Phase D to the mixture of Phases A, B and C obtained in step 3 and homogenize at 75°C + / - 5°C to obtain a mixture of Phases A, B, C and D. 5. Phase E ingredients were mixed and homogenized at 75°C + / - 5°C to obtain Phase E mixture. 6. The mixture of Phase E obtained in step 5 was added to the mixture of Phases A, B, C and D obtained in step 4, and homogenized at 75°C + / - 5°C to obtain a mixture of Phases A, B, C, D and E. 7. Add the ingredients of Phase F to the mixture of Phases A, B, C, D and E obtained in step 6, homogenize at 75°C + / - 5°C and then cool to room temperature.

[0383] All numerical values ​​for component amounts in Tables 1-5 are based on "wt %" of active material.

[0384] [Table 1A]

[0385] [Table 1B]

[0386] [Table 2A]

[0387] [Table 2B]

[0388] [Table 3A]

[0389] [Table 3B]

[0390] [Table 4A]

[0391] [Table 4B]

[0392] [Table 5A]

[0393] [Table 5B]

[0394] [evaluation] (moisturizing texture) Three panelists evaluated the texture of each of the compositions according to Examples 1 to 11 and Comparative Examples 1 to 13 from the perspective of moisturizing sensation during and after application of the composition. Specifically, each panelist applied each composition to their own hand, spread it, evaluated the moisturizing sensation, and ranked it from 1 (low) to 5 (high). The results were then classified into the following three categories based on the average grade: Good: 4~5 Normal: More than 2 and less than 4 Bad: 1~2

[0395] The results are shown in Table 6.

[0396] [Table 6]

[0397] Table 6 shows that compositions according to the present invention can provide improved moisturizing texture.

[0398] On the other hand, Table 6 also shows that compositions lacking any of the essential ingredients in the compositions according to the present invention can only provide limited or relatively poor moisturizing effects.

[0399] (Optical matte finish effect) The matte finish imparting effect of the compositions of Examples 3, 5, and 9-11 and Comparative Example 1 was evaluated by an in vitro matte finish imparting test. Specifically, each composition was spread over the entire contrast sheet using an automatic film applicator to form a 100 μm layer, which was then left to dry at 37° C. for 24 hours. Thereafter, an artificial sebum / sweat composition having the formulation shown in Table 7 below was sprayed onto the layer on the contrast card at room temperature. The amount of artificial sebum / sweat composition sprayed onto each of the layers was the same.

[0400] [Table 7]

[0401] After 6 minutes, the reflectance of the layer was measured as 60° gloss using a glossmeter (GM-268, manufactured by Konika Minolta).

[0402] The matte index was determined by the following formula: Matte index = {(reflectance of the above layer 6 minutes after spraying) - (reflectance of negative control)} / {(reflectance of positive control 6 minutes after spraying) - (reflectance of negative control)}*100

[0403] In the above formula, reflectance was set to 0 for the negative control and 100 for the positive control 6 minutes after spraying.

[0404] The determined matte index (%) was classified according to the following criteria: Excellent: 70 and above Good: 50 or above and below 70 Poor: Less than 50

[0405] The results are shown in Table 8.

[0406] [Table 8]

[0407] Table 8 shows that the composition according to the present invention can provide an excellent or good matte effect. In order to provide an excellent matte effect, it is preferable to use silica silylate as the (b) filler.

[0408] On the other hand, Table 8 also shows that (b) compositions lacking oil-absorbing powder as a filler cannot provide a matte feel-imparting effect.

Claims

1. (a) Below: (c) at least one cationic polymer selected from polyamines and at least one anionic polymer selected from hyaluronic acid and salts thereof; and At least one non-polymeric acid or salt thereof having two or more pKa values ​​selected from hydrophilic or water-soluble organic acids and salts thereof At least one particle comprising: (b) at least one filler selected from hydrophilic or hydrophobic oil-absorbing powders; (c) Water and A composition comprising: the hydrophilic oil-absorbing powder is selected from porous or hollow particles including cellulose, silica, perlite, talc, or mixtures thereof; the hydrophobic oil-absorbing powder is selected from porous or hollow particles containing hydrophobic silica; the amount of the (a) particle-forming cationic polymer in the composition is 0.01% by mass to 15% by mass, based on the total mass of the composition; the amount of the anionic polymer forming the particles (a) in the composition is 0.01% by mass to 15% by mass, based on the total mass of the composition; the amount of (a) particle-forming non-polymeric acid or salt thereof having two or more pKa values ​​in the composition is 0.01% by weight to 15% by weight based on the total weight of the composition; A composition, wherein the amount of the (b) filler in the composition is 0.01% by mass to 15% by mass, relative to the total mass of the composition.

2. The composition according to claim 1, wherein the amount of (a) the particle-forming cationic polymer in the composition is 0.05% by weight to 10% by weight, based on the total weight of the composition.

3. 3. The composition according to claim 1, wherein the amount of the anionic particle-forming polymer (a) in the composition is 0.05% by weight to 10% by weight, relative to the total weight of the composition.

4. 4. The composition of claim 1, wherein the non-polymeric acid or salt thereof having two or more pKa values ​​is phytic acid or a salt thereof.

5. 5. The composition according to claim 1, wherein the amount of the particle-forming non-polymeric acid or salt thereof having two or more pKa values ​​in the composition is 0.05% by weight to 10% by weight, based on the total weight of the composition.

6. The composition according to any one of claims 1 to 5, wherein the amount of the (a) particles in the composition is 0.01% by weight to 15% by weight, relative to the total weight of the composition.

7. 7. The composition according to claim 1, wherein the hydrophobic oil-absorbing powder is selected from silica silylate hydrophobic aerogel powders.

8. The composition according to any one of claims 1 to 7, wherein the amount of the (b) filler in the composition is 0.05% by mass to 10% by mass, relative to the total mass of the composition.

9. The composition according to any one of claims 1 to 8, wherein the amount of (c) water in the composition is 50% by mass to 95% by mass, based on the total mass of the composition.

10. 10. The composition according to claim 1, which is a cosmetic composition.

11. A cosmetic method for keratinous materials, comprising: applying a composition according to any one of claims 1 to 10 to keratinous materials; drying the composition to form a cosmetic film on the keratinous material; A method comprising:

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